Gluconic acid salts of certain oxyalkylated amine-modified thermoplastic phenol-aldehyde resins, and method of making same



United States Patent Ofiice 2,839,501 Patented June 17, 1958 GLUCONIC ACID SALTS OF CERTAIN QXYALKYL- ATED AMINE MODIFIED THERMOPLASTIC PHENOL-ALDEHYDE RESIN S, AND METHOD OF MAKING SAME Melvin De Groote, St. Louis, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Dela- Ware No Drawing. Original application January 26, 1953, Se-

rial No. 333,387, new Patent No. 2,771,446, dated November 20, 1956. Divided and this application April 9, 1956, Serial No. 576,823

13 Claims. (Cl. 260-53) The present invention is a continuation-in-part of my five co-pending applications, Serial No. 288,743, filed May 19, 1952, now abandoned; Serial No. 296,084, filed June 27, 1952, now U. S. Patent 2,679,485; Serial No. 301,804, filed July 30, 1952; Serial No. 310,552, filed September 19, 1952, now U. S. Patent 2,695,888; Serial No. 329,483, filed January 2, 1953; and a division of my co-pending application Serial No. 333,387, filed January 26, 1953, Patent No. 2,728,256.

My invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. My invention is also concerned with the application of such chemical products or compounds in various other arts and industries as Well as with methods of manufacturing the newchemical products or compounds which are of outstanding value in demulsification.

My aforementioned co-pending application, Serial No. 301,804, filed July 30, 1952, is concerned with the process of first condensing certain phenol-aldehyde resins, therein described in detail, with certain basic hydroxylated secondary monoarnines, therein described in detail, and formaldehyde, which condensation is followed by oXyalkylation with certain monoepoxides, also therein described in detail.

The present invention is concerned with the aforementioned amino resin condensate in the form of a gluconic acid, salt, i. e., a form in which part of or all the basic nitrogen atoms are neutralized with gluconic acid, i. e., converted into the salt of gluconic acid.

My aforementioned co-pending application, Serial No. 310,552, filed September 19, 1952, is concernedwith a process for breaking petroleum emulsions of the water-inoil type characterized by subjecting the emulsion to the action of a demulsifier including the amine resin condensates described in the aforementioned application Serial No. 301,804.

As far as the use of the herein described products go for purpose of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have sufficient 2 hydrophile character to meet at least the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally Xylene, is described as an index of surface activity.

The present invention involves the surface-activity of the gluconic acid salts, i. e., either where only one basic amino nitrogen atom is neutralized or where all basic amino nitrogen atoms are neutralized. Such gluconic acid salts may not necessarily be xylene-soluble. If such compounds are not Xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a watersoluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal Weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the heretofore appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For convenience, what is said hereinafter will be divided into eight parts:

Part 1 is concerned with the general structure of the amine-modified resins which after oxyalkylation are converted to the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with appropriate basic secondary hydroxylated amines which may be employed in the preparation of the herein described amine-modifiedresins;

Part 4 is concerned with reactions involving the'resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation;

Part 5 is concerned with the oxyalkylation of the products described in Part 4 preceding;

Part 6 is concerned with the conversion of the basic oxyalkylated derivatives described in Part 5, preceding; into the corresponding salt of giuconic acid;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products in the form of gluconic acid salts; and

Part 8 is concerned with uses for the products herein described, either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type, This part is limitedalso to the use of the gluconic acid salts.

For reasons which are obvious, particularly for convenience and ease of comparison, the various parts are in substantially verbatim form as they appear in one or more of the aforementioned co-pending applications, to wit, Serial Nos. 288,743, 296,084, 301,804, 310,552, and 329,483. For example, Parts 1, 2, 3 and 4 are substantially the same as it appears in aforementioned co-pending application, Serial No. 301,804, filed July 30, 1952, and Serial No. 310,552, filed September 19, 1952. Part 6 corresponds approximately to what appears in Serial No. 329,483, filed January 2, 1953.

PART 1 The compounds herein described and particularly useful as demulsifying agents are gluconic acid salts of the products obtained by oxyalkylating the amine resin condensates described in applications Serial Nos. 288,743 and 296,084 to which reference is made for a discussion of the general structure of such resins. These resins may be exemplified by an idealized formula which may, in part be an over-simplification in an effort to present certain resin structure. Such formula would be the following:

in which R represents any appropriate hydrocarbon radical such as an alkyl, alicyclic, arylalkyl radical, etc., with the proviso that at least one of the radicals designated by R has at least one hydroxyl radical. The hydrocarbon radical may have the carbon atom chain or equivalent interrupted by oxygen atoms. The only limitation is that the radical should not have a negative radical which considerably reduces the basicity of the amine, such as an aryl radical or an acyl radical. The introduction of two such amino radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be a counter-balancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. The presence of one or more hydroxyl radicals introduces a significant hydrophile effect. Finally, in such cases where R contains one or more oxygen atoms in the form of an ether linkage another effect is introduced, particularly another hydrophile eifect.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the

phenols themselves are difunctional phenols.

dissolve in one phase or the other.

4 I are difunctional from the standpoint of methylol-forming reactions. As is well known, although one may start with difunctional phenols, and depending on the procedure employed, one may obtain cross-linking which indicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta position. For instance in the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

The resins herein employed are soluble in a nonoxygenated hydrocarbon solvent, such as benzene or xylene. The resins herein employed as raw materials must be comparatively low molol products having on the average 3 to 6 nuclei per resin molecule.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is heatstable and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above C. without becoming an insoluble mass.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples inclined subsequently employ temperatures going up to to C.

What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 50 0, yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process is not intended to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available forfurther reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

PART 2 It is Well known that one can readily purchase on the open market, or prepare fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula 25'] OH H In the above formula 11 represents a small whole number varying from lto 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance or" low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

The resins herein employed as raw materials must he soluble in a nonoxyg'enated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are Xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No; 2,499,368 dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described pre viously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized over-simplification. previously referred to, the resultant product might be illustrated thus:

The basic hydroxylated amine may be designated thus:

In conducting reactions of this kind one does not necessarily obtain a hundred per cent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde or only one mole of the amine may combine with the resin molecule, or even to a very slight extent if at all, 2 resin units may combine Without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as. the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resinunitmay be exemplified thus:

in which R" is the divalent radical obtained from the particular aldehyde employed to formthe resin. For

reasons which are obvious the condensation product ob- 7 tained appears to be described best in terms of the method of manufacture,

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S.'Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without anycatalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a cat alyst, such strong acid should be neutralized. Siiniiarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I Mol. wt. Ex- Position R of resin ample R of R derived n molecule number om- (based on n+2) 1a Phenyi Para. Formal 3 992. 5

Mixed secondary Ortho...

and tertiary amyl.

Propyl Tertiary hcxyl Oct 1 Parau" Dodecyl.. Tertiary butyl mmmcncwmcn umcumm Tertiary amyl.

Tertiary amyl N onyl Tertiary butyl Tertiary amy] N onyl Tertiary butyl Tertiary amyl 8 PART 3 As has been pointed out previously the amine herein employed as a reactant is a basic hydroxylated secondary f, monoamine whose composition is indicated thus:

in which R represents :a monovalent alkyl, alicyclic, arylalkyl radical which may be heterocyclic in a few instances as in a secondary amine derived from furfurylamine by reaction of ethylene oxide or propylene oxide. Furthermore, at least one of the radicals designated by R must have at least one hydroxyl radical. A large number of secondary amines are available and may be suitably employed as reactants for the present purpose. Among others, one may employ diethanolamine, methyl ethanolamine, dipropanolamine and ethylpropanolamine. Other suitable secondary amines are obtained, of course,

by taking any suitable primary amine, such as an alkylamine, an arylallcylamine, or an alicyclic amine, and treating the amine with one mole of an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide. Suitable primary amines which can be so converted into secondary amines, include butylarnine, arnylarnine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine, etc. In other instances secondary amines which have at least one hydroxyl radical can be treated similarly with an oxyalkylating agent, or, for that matter, with an alkylating agent such as benzylchloride, esters of chloroacetic acid, alkyl bromides, dirnethylsulfate, esters of sulfonic acid, etc., so as to convert the primary amine into a secondary amine. Among others, such amines include 2-amino-lbutanol, Z-amino-Z-methyl-l-propanol, 2-amino-2-methyl-l,3-propanediol, 2-amino-2-ethyl-1,3-propanedio1, and tris(hydroxymethyl)-aminomethane. Another example of such amines is illustrated by 4-amino-4-rnethyl-2- pentanol.

Similarly, one can prepare suitable secondary amines which have not only a hydroxyl group but also one or more divalent oxygen linkages as part of an ether radical. The preparation of such amines or suitable reactants for preparing them has been described in the literature and particularly in two United States patents, to wit, U. S. Patents Nos. 2,325,514 dated July 27, 1943, to Hester, and 2,355,337 dated August 8, 1944, to Spence. The latter patent describes typical haloalkyl ethers such as onto orator CH2 CH-CH2O 021140 C2H4Br CzHsO CiiHiO 021140 (321140 CzHiCl Such haloakyl ethers can be reacted with ammonia droxyl radical but a repetitious ether linkage. Compounds can be readily obtained which are exemplified by the following formulas:

(CzHsO 02114002114) NH HO C2H4/ HO CaHi (C4H9OCH2CH(CH:)O(GHQCHCHa) 1100911. ontoomonqoomomoomom) Home, onto0H2olzoorno11,011,011?)v p HOCQHA or comparable compounds having two hydroxyl-ated groups of dilferent lengths as in (H0 OHzCHgO CHziCHzO CHzCHr) HOCnH4 Other examples of suitable amines include alpha-methylbenzylamine and monoethanolamine; also amines obtained by treating cyclohexylmethylamine with one mole of an oxyalkylating agent as previously described; betaethylhexyl-butanolamine, diglycerylamine, etc. Another type of amine which is of particular interest because it includes a very definite hydrophile group includes sugar amines such as glucamine, galactamine and fructamine, such as N-hydroxyethylglucamine, N-hydroxyethylgalactamine, and N-hydroxyethylfructamine.

Other suitable amines may be illustrated by CH3 HO.CH2..CH2OH 11m nocmcornon CHt CHallCHaOH r'rn CH3..CH2OH 3133 See, also, corresponding hydroxylated amines which can be obtained from resin or similar raw materials and described in U. S. Patent No. 2,510,063, dated June 6, 1950, to Bried. Still other examples are illustrated by treatment of certain secondary amines, such as the following, with a mole of an oxyalkylating agent as described; phenoxyethylamine, phenoxyalphamethylethylamine, and phenoxypropylamine.

Other procedures for production of suitable compounds having a hydroxyl group and a single basic amino nitrogen atom can be obtained from any suitable alcohol or the like by reaction with a reagent which contains an epoxide group and a secondary amine group. Such reactants are described, for example, in U. S. Patents Nos. 1,977,251 and 1,977,253, both dated October 16, 1934,

It) to Stallmann. Among the reactants described in said latter patent are the following:

PART 4 hyde is described in detail in applications Serial Nos.

288,743 and 296,084, and reference is made to those applications for a discussion of the factors involved.

Little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration: 1

Example lb The phenolaaldehde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a, preceding, were powdered and mixed with 700 grams of xylene. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C. and 210 grams of diethanolamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde used was a 37% solution and 160 grams were used which were added in about 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C. for about 21 hours. At the end of this period of time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time and the presence of unreacted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within approximately 3 hours after the refluxing was started. As :soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached about C. The mass was kept at this higher temperature for about 3% hours and reaction stopped. During this time any additional water which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of \a sticky fluid or a tacky resin. The overall reaction time was a little over 30 hours. In other instances it has varied from approximately 24 to 36 hours. The time can be reduced by cutting the low temperature period to about 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed 12 until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the Water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

TABLE II Strength of Reac- Reac- Max. Ex Resin Amt., tormal- Solvent used tlon tion dis- No used grs. Amine used and amount dehyde and amt. temp., time, tillv soln. and 0. (hrs) temp,

amt. C.

882 Diethanolarnine, 210 g 37%, 162 g". Xylene, 700 g 22-26 32 137 480 Diethanolamlne, 105 g. Xylene, 450 g... 21-23 28 150 633 do Xylene, 600 g.--- 20-22 36 145 441 Dipropanolamine, 133 g Xylene, 400 g. 20-23 34 146 480 do' Xylene, 450 g 21-23 24 141 633 do Xylene, 600 g.... 21-28 24 145 882 Ethylethanolamine, 178 g Xylene, 700 g.- 20-26 24 152 480 Ethylethanolamine, 89 g Xylene, 450 g. 24-30 28 151 633 do Xylene, 600 g.... 22-25. 27 147 473 Cyclohexylethanolamine, 143 g Xylene, 450 g.... 21-31 31 146 511 do d 22-23 36 148 665 do ....-d0 Xylene, 550 g.... 20-24 27 152 C2H5002H4002H4 13m... 21... 441 NH, 176 g "do Xylene, 400 gm. 21-25 24 150 CnHsOCzH4OC2H4 14b a 480 NH, 176 g d0 Xylene, 450 g.... 20-25 26 146 OzH5OCzH4OCzH4 15b 9a 595 NH, 176 g "don..." Xylene, 550 g. 21-27 30 147 HOCZHA V HOC2H1OCzH4OCzH4 16b. 2a... 441 NH, 192 g .-d0 Xylene, 400 g.... -22 148 HOCZHA HOOQH4OG2H4OC2H4 17b 5a.-- 480 NH, 192 g do d0 20-25 28 150 HOC1H4 HOO2H4OC2H4OC2H4 18b.. 14a.... 591 NH, 192 g d0 Xylene, 500 g.... 21-24 32 149 HOCZH4 HOCzH4OG2H OCzH4 19b. 22a 498 NH, 192 g ..d0 Xylene, 450 g.... 22-25 32 153 HOCQH;

QH (OC2H4): 20b. 2311.... 542 NH, 206 g 30%, g..- Xylene, 500 g. 21-23 36 151 HOO2H4 CH:(O 021103 21b. 25a. 547 NH, 206 g -.d0 25-30 34 148 HOC2H4 OH (OO2H4)3 22b 2a"..- 441 NH, 206 g d0 Xylene, 400 gm. 22-23 31 146 I HOOzHi 2%.... 26am. 595 Decylethanolam'me, 201 g 37%, 81 g.... Xylene, 500 g 22-27 24 241).... 27a 391 Decylethanolamine, 100 g 30%, 50 g. Xylene, 300 g.. 21-25 26 147 PART propylation step insofar that two low boiling liquids are handled in each instance. What immediately follows refers to oxyethylationand it is understood'that oxypropylation can be handled conveniently in exactly the samernanner. 'The oxyalkylation of 'the amine resin condensates is carried out by procedures whichare commonly used for the oxyalkylation of oxyalkylation susceptible materials. T he factors to be consideredare discussed in some detail in applications Serial Nos. 301,804 an'd 3l0,552 and reference is made to those applications for a description of suitable equipment, precautions to be taken and ageneral discussion of operating technique.

The following examplesaregiven by way of illustration.

Exa rr tp le 1c The oxyalkylation susceptible compound employed is the one'previously described and designated as Example 111. Condensate 1b was in turn obtained from diethanolamine and the resin previously identified as Example 2a. Reference to Table I shows thatthis particular'resin is obtained from paratertiarybutylphenol and formaldehyde. 11.16 pounds ofthis resin condensate were dissolved in 7 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximatly125 C. to 135 C., and at apressureof about to pounds.

The time regulator was set so as 'to inject the ethylene oxide inapproximately two hours and then continue stirring for a half-hour'or longer. Thereaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. More specifically itwas complete in 45 minutes. The speed of reaction,-particularly at the low pressure, undoubtedly' was due ina large measure to excellentagitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 11.16 pounds. This represented a molal ratio of moles of ethylene oxide per mole of condensate.

The theoretical molecular w'eight at the end of the reaction period was 2232. A comparatively small sample,

less than 50 grams, was withdrawnmerely for examination as faras solubility or'emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in thedata, orsubsequent data, or inthe data presented in tabular form in subsequent Tahles III and IV.

The size of the autoclave employed was'25"gallons.

14 In innumerable comparable oxyalkylations I have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as herein afternoted and subjected to oxyalkylation with a diiierent oxide.

Example 20 This example simply'illustrates the further oxyalkylation of Example 10, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example 1b, present at the beginning of the stage was obviously the same as at the end of the pri'or stage (Example 1c),

to wit, 11.16 pounds. The amount of oxide present in the initial step was 11.16 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount ofsolvent remained the same. The amount of oxide added was another 11.16 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 22.32 pounds and the molal ratio of ethylene oxide to resin condensate was 50.8 to 1. The theoretical molecular weight was 3348.

The maximum temperature during the operation was C. to C. The maximum pressure was in the range of 15 to 20 pounds. The time period was one hour.

Example 30 The oxyalkylation proceeded in the same manner described in Examples 1c and 2c. There was no added solvent and noadded catalyst. The oxide added was 11.16 pounds and the total oxide at the end of the oxyethylation step was 33.48 pounds. The molal ratio of oxide to condensate was 76.2 to 1. Conditions as far as temperature and pressure and time were concerned were all the sameas in Examples 1e and 2c. The time period was somewhat longer than in previous examples, to wit, 2 hours.

Example 4c The oxyethylation was continued and the amount of oxide'added again was 11.16 pounds. There was no added catalyst and no added solvent. The theoretical molecular weight at the endof the reaction period was 5580. The molal ratio of oxide to condensate was 101.6 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 3 /2 hours. The reaction unquestionably began to slow up somewhat.

Example 50 The oxyethylation continued with the introduction of another 11.16 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added; The theoretical molecular weight at the end of the agitation period was 6696', and the molal ratio of oxide to resin condensate was 127 to 1. The time period, however,

dropped to 1 /2 hours. Operating temperature and pressure remained the same as in the previous example.

Example 60 The same procedure was followed as in the previous examples except that an added 4 pound of powdered caustic soda was introduced to speed up the reaction. The amount of oxide added was another 11.16 pounds, bringing the total oxide introduced to 66.96 pounds. The temperature and pressure during this period were the same as before. There was no added catalyst and also no added solvent. The time period was 2 /2 hours.

Example 70 The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period .was 78.12 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8928. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 3 hours.

Example 80 This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount ofoxide added at the end of this step was 89.28 pounds. The theoretical molecular Weight was 10,044. The molal ratio of oxide to resin condensate was 203.2 to one. Condition as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 4 hours.

The same procedures as described in the previous examples are employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a ZS-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a IS-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 10 through 400 were obtained by the use of ethylene oxide, whereas 410 through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows.

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Example 10 through 40c, the amount of oxide present in the oxyalkylation derivatives is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored where a single oxide was employed.

The 9th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction per-1o Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 10, 2b, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third col- .umn gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the S01 vent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively, small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV, Examples 410 through c are the counterparts of Examples 1c through 400, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, four columns are blank, to wit, columns 4, 8, 11 and 15.

Reference is now made to Table V. It is to be noted these compounds are designated by d numbers, 1d, 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the c series, for example, 350, 39c, 53c. and 62c. These compounds involve the use of both ethylene oxide and propylene oxide. Since compoundslc through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from 350 and 390, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, those compounds obtained from 530 and 620 obviously came from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial 0 series such as 35c, 39c, 53c, and 620, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with ld, it will be noted that the initial product, i. e.,' 350, consisted of the reaction product involving 11.16 pounds of the resin condensate, 16.74 pounds of ethylene oxide, 1.0 pound of caustic soda, and 7.0 pounds of the solvent,

It is to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the' solvent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any. i

2,889,501 17 18 In this series, it will be noted that the theoretical mois used along with either one of the two oxides just menlccular weights are given prior to the oxyalkylation step tioned, or a combination of both of them. i and after the oxyalkylation step, although the value at The colors of the products usually vary from a reddish the end of one step is the value at the beginning of the amber tint to a definitely red, and amber. The reason next step, except obviously at the very start the value 5 is primarily that no effort is made to obtain colorless w .m m m mmm m g n m.I e f be o h wm uem m ou m vnmhmbmcwm emfi as... m ar fimnom b fl mmmwnfl wt. le m wemm mmw O11 .1 u mn oemltw n r wo St ed pe t earim0 le r.. u w w i .m Wma em s W e m h. yl h 1 .1 m d .1 0 PH.H 6 m e n rm mw ue m o e I t. SSHI1MEBBYE; 5 m .s u mmbb mann mdm m m m m m me l emn m mm m m mkmme mmtm am d v fkm amn nm m m ms h tnm d m A Me y ne h .1 mo a ow m u m r m c n i O p B y S l S t e i m reo a sw e u ,muqwm .mbmms wwmm m a S 0 r r r ma anmwmopw mpmo 0 w 1 dm m w m we mtmnm wwwmmw H O6 0618M... mmmm hm a m mm mwr d mfH fl l n so nw One a1 m mm m d a e gs w w7md mwmmmm w em se u mc pm el mh m fiw map mflfl l .m 0 en n. .n d .i w ma emwmmod 1E n r m m S S VI 0 .I. u e e m m mm w e w m mm n o bfihfiv .m w t. sgre nm momm m m omm o m m wm m x imsn m vs m n mmm o ee v. m o wmmmw 6 0 y U. .1 m m ni b ald tu Ouh oa c nu n l mr ec .l Ufl 0 d t P O S V a d O W H 311 V e sde em 0 wmmtmen esy Wfd fl U m m dol vd s mvml the the ydro- Molec. wt.

oretical value Propl. based oxide on theuseept.

cmpd.

Molalratlo Ethyl. toxide t 00x o ox alkyl alkl:

gt. s emp 50617273864300674938382687 4219825803691 92 7925 1479312356780 m nnm nnnwn inii 11112 i 000000005555555.0000000005555555500000000 7 7 7 7 7 7 7 7 A-A44 4nmLLZZZ-LlllliikiidfmdI/ZZZ7777 product. the amount ,of alkaline catal t gen atom, the removal of lyst,

0000333300003333000033330000333300003333 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLILLL Composition at and pi. Cataoxide,

oxide,

Generally speaking,

e catalyst is somewhat more difficult than ordi- O-S' Ethl. Pro cmpd, lbs.

44 44446666666666666666 wwm l wmmwmwwwwwmwfi88u8888fifi55566511111111 0 QU 0 22 2 2 2 22ZLLLLLLLL nuuuuunummmmmmmmwwwml1111111111111111111 the cost of bleaching the present is comparatively small and it need not be removed. Since the products per se are alkaline due to presence of :a basic nitro 'alkalin chloric acid, for example, to 11 may partially neutralize the -b The preferred procedure is to alkali unless it is objectionab metric amount of concentrat to the caustic soda present.

vent,

s and TABLE III Catalyst, v s.

00.00333300003333000.033330000333300003333 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL oxide, if mployed.

oxyalkyland then the 25 narily is the ease for the reason that if one adds h opl. oxide,

go back to ethylpropylene oxide;

Composition before Ethl. Pr oxide,

i 48 6048 62 4062 8642086 6 67 257 0123455 2670257 5162739 nnmnauufifiwm "H23m67oe 1234567 m1235678 112233 ylene oxide and propylene lbs.

00 0 44444 4 6668666666666666 wmmwwwwmmmm-flku -W-bm soooooooomss-ofi-b b flfi-b11111111 s .QQZZZZZZZZLLLLLLLL nuuunnnunmmmmummwwwlwwl11.111111111111111 start with propylene oxide, then cmpd., cmpd.,

one could start with ethylene oxide Ex. NO.

move traces or small amounts of uncombined present and volatile under the conditions e Obviously, in the use of eth oxide in combination one need not first use one oxide and then the other, but one can mix the two oxide thus obtain what may be termed an indifferent tion, i. e., no attempt to selectively add one a other, or any other variant.

Needless to say, and then use propylene oxide, and then ene oxide; or, inversely, use ethylene oxide, and then go back to or, one could use a combination in which butylene oxide Oxyalkylation-susceptible.

TABLE VI Max. pres., Time, 1). s. 1.

hrs.

S olubility Water Xylene Kerosene Insoluble Emulsifiable. S luble Insoluble Emulslfiable. Solubl llllllillllllll o. Insoluble. D

Insoluble. Dlspersible. Solubl e. Do.

0. Insoluble. Dispersible.

0. oluble.

D0. Dlspersible. Soluble.

Do. Do.

D o. Insoluble.

Insoluble.

D 0. Dlspersible. Insoluble.

Do. Do. Do.

TABLE VIP-Continued Max. Max Solubility Ex temp., pres, Time, No 0. p. s. hrs.

Water Xylene Kerosene -10 bi Insoluble Soluble. 5-10 1 do Do. 510 1% Emulsifiable Do. 5-10 254mm) Do. 6-10 3% Dlspersible. 5-10 3 Insoluble. 5-10 3% Do. 6-10 2% Do.

PART 6 the oxyalkylated derivatlve by use of vacuum distilla- The conversion of the oxyalkylated basic condensates of the kind previously described into the corresponding salt of gluconic acid is a simple operation since it is nothing more nor less than neutralization. The condensate invariably contains two basic nitrogen atoms. One can neutralize either one or both nitrogen atoms.

Another factor which requires some consideration would be the presence of basic catalysts which were used during the oxyalkylation process. Actual tests indicate that the basicity appears to be somewhat less than would be expected, particularly in examples in which Oxyalkylation is comparatively high. The usual procedure has been to add enough glutonic acid to convert the product into the salt as predetermined and the note whether or not the product showed any marked alkalinity. If so, slightly more gluconic acid was added until the product was either just barely acid or just very moderately alkaline. For sake of clarity this added amount of gluconic acid, it required, is ignored in subsequent Table No. VIII.

Gluconic acid is available as a 50% solution. Dehydration causes decomposition. This is not true of the salts or, at least, the salts of the hereindescribed oxyalkylated condensates. Such salts appear to be stable, or stable for all practical purposes, at least at a temperature slightly above the boiling point of water and perhaps at a temperature as high as 150 C. or thereabouts.

As has been pointed out previously the present application is a continuation-impart of certain co-pending applications and reference is made to aforementioned co-pending application, Serial No. 329,483, filed January 2, 1953. The co-pending application, Serial No. 329,483, filed January 2, 1953, describes the neutralization of the nonoxyalkylated condensate. Reference nowv is made to Table VII which, in essence, is substantially the same as much of the data in Table II but includes additional calculations showing the amount of gluconic acid (50%) required to neutralize a certain amount of condensate, for instance, compare Example 1e in Table VII with Example lb in Table II. In any event since there were available various oxyalkylated derivatives of condensates lb, 5b, and 7b, these particular oxyalkylated derivatives were used for the purpose of illustrating a salt formation, all of which is illustrated in Table VIII.

Briefly stated, referring to Example 11'', Table VIII, it is to be noted that 1116 grams of the nonoxylalkylated condensate required 756 grams of 50% gluconic acid for neutralization. Reference to Table VIII shows that 1116 grams of the condensate lb when convertedinto the oxyal kylated derivative as obtained from 30 were equivalent to 5150 grams. Therefore, 5150 grams were selected as the appropriate amount of oxyalkylated material for neutralization simply for the reason that calculation was eliminated.

The oxyalkylated condensate generally is a liquid and,

as a rule, contains a comparatively small amount of solvent. Note the examples in Table VIII. The solvent happened to be xylene in this instance but could have been benzene, aromatic petroleum solvent, or the like. Need-' less to say, the solvent could have been removed from tion and this is particularly true if benzene happened to be the solvent. The product obtained from oxyalklyation is invariably lighter than the initial material for the reason that the condensate is dark colored and Oxyalkylation simply dilutes the color. In other words, the product may be almost white, pale straw color or amber shade with a reddish tint.

The product either before or after neutralization can be bleached with filtering clays, charcoals, etc. The procedure generally is, as a matter of convenience, to

, form the salt and then dilute with a solvent if desired,

using such solvent as Xylene or a mixture of two-thirds xylene and one-third ethyl alcohol or isopropyl alcohol, to give approximately a 50% solution.

If desired, the product prior to dilution could be rendered anhydrous simply by adding benzene and subjecting the mixture to reflux acition under a condensate or a phase-separating trap. If there happened to be any tendency for the product to separate then the solvents having hydrotropic I properties, such as the diethylether of ethylene-glycol, or

the like are used; I

The salt formation is rnerely a matter of agitation at room temperature, or at a somewhat higher temperature Usually agitation is continued for an hour but actually neutraliza- 11 tion may be a matter of minutes.

sa'lt formation is complete and the product is diluted to approximately 50%, I have permitted the solution to In some instances after stand for about 6 to 72 hours. Sometimes, depending on f composition, there is a separation of an aqueous phase 7 almost solid or tacky. terials to viscous liquids or thin liquids comparable to polyor a small amount of salt-like material. On a laboratory scale the procedure is conducted in a separatory funnel. If there is separation of an aqueous phase, or any other undesirable material, at the bottom of the separatory funnel it is merely discarded. The salt form, of course, can be bleached in the same manner as previously described for the oxyalkylated derivative. Usually the color of the salt is practically the same as the oxyalkylated derivative. For various commercial purposes in which the product is used there is no justification for the added cost of decolorization. The salt form can be dehydrated or rendered solvent-free by the usual procedure, i. e., vacuum distillation, after the use of a phase-separating trap.

The product as prepared, without attempting to decolorize, eliminate any residual catalyst in the form of i a salt, and without any particular effort to obtain absolute neutrality or the equivalent, is more satisfactory for a number of purposes where the material is useful, such as a demulsifier for petroleum emulsions of the water-in-oil type, or oil-in-water type; or in the prevention of corrosion of metallic surfaces, especially ferrous surfaces; or

as an asphalt additive for anti-stripping purposes.

The condensates prior to oxyalkylation may be solids but are generally viscous liquids or liquids which are Oxyalkylation reduces such maglycols, of course depending primarily on the amount. of alkylene oxide added. After neutralization the physical characteristics of the products are about the same and in If there happened to be any precipitate the solution is filtered.

the majority of cases are liquids. Needless to say, if a sol. vent were added, even if the material were solid initially, it would be converted into a liquid form.

In light of what has been said and the simplicity of salt formation it does not appear that any illustration is 26 separatory funnel. To this there were added 756 gran-is of gluconic acid and the mixture stirred vigorously for an hour and allowed to stand at room temperature, or slightly above, for approximately two days. The slight 6 amount of dregs at the bottom was withdrawn and the marequlred- However, Prevlous refarfmce has been made teria'l stored as such, although subsequently it was d1luted to Table VIII. The first example in Table VIII 1s EX- to approximately with xylene and employed in the ample 1 The following 18 more specific data in regard form of a 50% solution to Example E l 1 A number of other examples are included in Table VIII.

xamp e f 10 For convemence, Table VII 18 included at this point The salt was made from oxyalkylated derivative Ex- ]1]St preceding Table VIII.

TABLE VII Salt formation calculated on Condensate in turn derived irorn basis of non-oxyalkylated Salt condensate from Salt con- Ex. den- 37% Wt. of N o. sate Amt. Amt. Amine formconden- Then. 50% glu- No. Resin resin, Solvent sol- Amine used used, aldesate on basic conic No. gins. vent, gms. hyde, solventnitrogen, acid, gins. gms. iree basis, gins. gms.

gms.

882 Xylene. S82 Diethanoletnine 210 162 1,116 27.0 756 480 do.... 480 .do 81 597 13.5 378 633 do 63 105 81 750 13.5 378 44-1 do 133 100 586 13.6 380 480 do. 133 100 625 13.6 380 633 633 do 133 100 778 13.6 380 882 do... 882 Ethylethanolamine 178 162 1, 084 28.0 784 480 do. 480 do 89 81 581 14.0 392 633 do 633 dO 89 81 734 14.0 392 473 do 473 Cyclohexylethanolaminm. 143 100 671 14.0 392 511 do..... 511 .do 143 81 728 14.0 392 665 ..do. 81 882 14.0 392 882 do. 162 1,116 27.0 378 441 do 100 586 13.5 189 882 .do. 162 1,084 28.0 392 30% formaldehyde.

TABLE VIII Grams oi oxyalkylated compound Obtained in turn from- Percent which is equiv. 50 percent Oxyalkyleondento grams of congluconic Ex. N 0. ated desate in densate acid to rivative, oxyalkylneutralex. No. I nted deize, grams Conden- Amt.con- EtO PrO Solvent rivative Oxyalkyl- Condensate, densate, amt, amt., emu, ated comsate ex. N 0 lbs. lbs. lbs. lbs. pound ample 3c. Oxyalkylated derivative 30, in turn, was made PART 7 from condensate Example 1b. Condensate Example 1b, in turn, was made from resin Example 2a and diethanolamine. 882 grams of the resin were dissolved in approximately an equal weight of xylene and reacted with 210 grams of diethanolamine and 162 grams of 37% formaldehyde. All this has been described previously. The weight of the condensate on a solvent-free basis was 1116 grams. This represented approximately 27 grams of basic nitrogen. Referring to Table VIII it will be noted that 11.16 pounds of condensate were combined with 33.48 pounds of ethylene oxide in combination with 7 pounds of solvent. In any event, 5150 grams of oxyalkylated derivative 3c were placed in a laboratory device Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as Water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed which, although made of metal, was the equivalent of a 7 as the demulsifying agent of my process may be admixed 'nection with conventional demulsifying agents.

, 27 with one or more of the solvents customarily used ilfi/[COII- ore' over, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials of my invention when employed as demulsifying agents.

The materials of my invention, when employed as treating or dernulsifying agents, are used in the conventional way, well known to the art,'described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of dernulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

As noted above, the products herein described may be A mixture PART 8 The gluconic acid salts herein described can be used as emulsifying agents for oils, fats and waxes; as ingredients in. insecticide compositions; or as detergents and wetting agents in the laundering, scouring, dyeingJan They also-ca'n'be used for preparing boring or metabcutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes? Also, the gluconic acid salts are useful in dry ning and mordanting industries.

cleaners soaps.

Also, they may beused as additives in connection with other emulsifying agents; they may be used to contribute hydrotropic effects; they may be used as anti-strippers in connection with asphalts; they may be used to prevent corrosion particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas, and also in refineries where crude oil is converted into various commercial products. The products may be used industrially to inhibit or stop 'microorganic growth or other objectionable lower forms of life, such as the growth of bacteria, molds, etc.; they are valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils, and also to hydraulic brake fluids of the aqueous or nonaqueous type; some have definite anti-corrosive action. They may be used in connection with other processes used not only in diluted form, but also may be used admixed with some other chemical demul sifier; "which illustrates such combination is thefollowing:

fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters.

After oxyalkylation a condensate of the kind previously described becomes a derivative which retains basic nitrogen radicals and also includes alkanol radicals, such as the hydroxyethyl or hydroxypropyl radical. Thus, in attempting to dehydrate the oxyalkylated salt derived from gluconic acid or merely by heating there may be a rearrangement wherein one forms the ester in the same manner that triethanolamine oleate can be converted into oleyl triethanolamine. Thus the compounds described may serve as precursors for other derivatives obtained by esterification. In fact, any reference to decomposition on heating must of necessity include such possibility.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent is:

l. A three-step manufacturing process including the method of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula atoms in any group attached to the amino nitrogen atom,

and (c) formaldehyde; said condensation reaction being conductedv at a temperature sufficiently high to eliminate A water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule thy virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom v ith.-aresin"'-molecule; and with the furtheruproviso th at the resinous condensatignproduct resulting from the process be heat-stable andoxyalkylation-susceptible; followed by an oxyalkylaof removing a mud sheath, increasing the ultimate flow of tion step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by 'the third step ofn'eutralizing with gluconic acid.

2. A three-step manufacturing process including the method of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6. position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin'mole cule; with the further proviso that the molar ratio of reactants be approximately 1, 2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

3. A three-step manufacturing process including the method of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the suhsttantial absence of tritunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

4. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from. the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

5. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of Water and below C., with the proviso that the con densation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldchyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible, followed by an oxyalkylation step by means of an alpha'beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

6. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, Water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a para-substituted aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms; (12) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen 'atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent;

.ene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

7. The manufacturing procedure of claim 1 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

. 8. The manufacturing procedure of claim 2 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

9. The manufacturing procedure of claim 3 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

10. The manufacturing procedure of claim 4 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

11. The manufacturing procedure of claim 5 wherein the oxyalkylation step is limited to thevuse of both ethylene oxide and propylene oxide in combination.

12. The manufacturing procedure of claim 6 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

13. The product resulting from the three-step manufacturing procedure defined in claim 1.

References Cited in the tile of this patent UNITED STATES PATENTS 2,031,557 Bruson Feb. 18, 1936 2,743,252 De Groote .-Apr. 24, 1956 

1. A THREE-STEP MANUFACTURING PROCESS INCLUDING THE METHOD OF FIRST CONDENSATING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NECLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLO-FORMING REACTITIVY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIS BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 